Protocol Gas Verification Program (PGVP) Michael Hayes ICAC/ MARAMA Workshop Advances in Control Technologies July 9-10, 2008 Exton, PA
PGVP Protocol Gases from an historic perspective Historical Audit The PGVP
Protocol Gases From an Historic Perspective GENESIS IN the beginning the Lord created
Protocol Gases From an Historic Perspective Calibration of CEMS to NIST traceable standards Only traceable standards available were SRMs SRMs only available in limited quantities and or concentrations also small cylinder (800 l) EPA and NIST developed EPA Traceability Protocol For Assay And Certification Of Gaseous Calibration Standards
Protocol Gases From an Historic Perspective The Green Book
Protocol Gases From an Historic Perspective
Protocol Gases From an Historic Perspective Primary Standard SRM Standard Reference Material NTRM NIST Traceable Reference Material GMIS Gas Manufacturer s Internal Standard
Primary Standard Produced by NIST using gravimetric procedures Analyzed via two or more independent methods over time to confirm concentration Maintained at NIST (Gaithersburg, MD)
Standard Reference Material Produced under contract to NIST by a specialty gas company (currently only two companies manufacture for NIST) NIST analyzes each cylinder over time to confirm concentration. Analysis is directly traceable to PRM. Sold by NIST
NIST Traceable Reference Material Produced by a Specialty Gas Manufacturer in a batch; for cylinder to cylinder homogeneity (currently 4 companies produce NTRMs) Cylinders are analyzed over time Data is reported to NIST NIST requests at least 10% of the batch be sent to NIST and NIST performs its own analysis NIST names the batch NTRMs can have less uncertainty than SRMs
NIST Traceable Reference Material
Gas Manufacturer s Internal Standard Produced by a Specialty Gas Manufacturer following the Green Book Cylinders are analyzed over time vs. SRM or NTRM following the Green Book Cylinder is named by manufacturer
Protocol Gases From an Historic RGM Research Gas Material NIST named cylinder for which there is not the demand and/or the politics to have an SRM. NTRM Prime Perspective Similar to NTRMs except NIST analyzes and names each cylinder. Driven by the auto industry to minimize uncertainty of tail pipe emissions data
Protocol Gas Manufactured and analyzed following the green book. Single analysis for non-reactives Dual analysis one week apart for reactives Analyzed against SRM NTRM / NTRM Prime / RGM GMIS
Minimum Requirements for U.S. EPA Protocol Gases The following is the minimum information to be included when reviewing the certification documentation for U.S. EPA Protocol gases. 1. Cylinder identification number (serial number). 2. Certified concentration within three digits of the standard (ppm or % -mole basis). 3. Balance gas in the standard mixture. 4. Cylinder pressure at time of certification. 5. Assay/Certification date. 6. Certification expiration date. 7. Reference standard identification (standard type [SRM, PRM, NTRM, or GMIS], cylinder number and concentration). 8. Statement that the assay/certification conforms to EPA protocol guidelines. 9. Analytical method used. 10. Laboratory identification number (laboratory name, laboratory address). 11. Chronology of previous EPA protocol gas certification for this cylinder. 12. Analytical accuracy of the mixture. 13. Statement that certification was corrected for interference's (if applicable). 14. Ensure the concentration certified by the vendor matches the cylinder label value.
Audit History of Protocols 1970 s -1996 EPA audited gases Posted results In 1995, one vendor off by -16.3% (CEM would underreport) Strong utility and vendor support Auditing strongly correlated with improved gas quality Audit discontinued after 1996 due to budgetary constraints Audit reinitiated in 2003
2002 2003 2001 30 25 20 15 10 5 0 Audit Results 1994 1995 1996 1997 1998 1999 2000 1993 1992 % Failures
2003 Gas Audit First audit in 7 years Blind audit 14 national gas vendors Similar procedures as in past SRMs and NTRMs used 42 Protocol tri-blend cylinders
Results Overall failure rate: 14 of 126 analyses (11%) 57% of vendors failed SO 2 : Worst tag value ~2.5% high NO: Worst tag value ~8% low CO 2 : Worst tag value ~4.9% high All 42 cylinders met the Protocol Procedure documentation requirements
2002 2003 2001 30 25 20 15 10 5 0 Audit Results 1994 1995 1996 1997 1998 1999 2000 1993 1992 % Failures
EPA wants to improve and maintain the quality of US EPA Protocol gases thus PGVP
Part 58 (ambient) 1/17/06 Gaseous pollutant concentration standards (permeation devices or cylinders of compressed gas) used to obtain test concentrations for CO, SO 2, NO, and NO 2 must be traceable to either a National Institute of Standards and Technology (NIST) Traceable Reference Material (NTRM) or a NISTcertified Gas Manufacturer's Internal Standard (GMIS), certified in accordance with one of the procedures given in reference 4 of this appendix. Vendors advertising certification with the procedures provided in reference 4 of this appendix and distributing gasses as EPA Protocol Gas must participate in the EPA Protocol Gas Verification Program or not use EPA in any form of advertising.
Part 72 & 75 (stack) 1/24/08
EPA PGVP Contractor
Thank you! Questions?